Nail color coating system

ABSTRACT

A nail polish composition containing a crosslinkable coating composition. The composition comprises ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and a carbonate initiator of Formula (1) 
     
       
         
         
             
             
         
       
     
     wherein R 7  is selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms; and A n+  is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A n+  is not an acidic hydrogen; at least one colorant independently selected from the group consisting of (i) a dye; (ii) an inorganic pigment; or an (iii) a lake; and optionally further comprising ammonium carbamate (H 2 NR 8 R 9 +—OC═ONR 8 R 9 ), wherein R 8  R 9  are each independently selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority benefit from U.S. Provisional Patent Application 62/518,791 filed Jun. 13, 2017 which is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The invention provides for a crosslinkable composition for use in nail coating compositions containing dyes, inorganic pigments or lakes.

BACKGROUND

The coatings industry continues to develop new chemistries as performance requirements for decorative and functional coatings evolve. Drivers for change are varied and these can include: regulatory controls to reduce VOC emissions, concerns about toxic hazards of coating raw materials, a desire for cost reduction, commitments to sustainability, and a need for increased product effectiveness.

UV nail gel coatings have gained rapid popularity with fashion conscious individuals who apply nail polish to fingernails or toenails to decorate and protect nail plates. UV nail gels can produce coatings that exhibit phenomenal chip resistance and durability when properly applied and cured in comparison to those nail coatings derived from traditional solvent based nail lacquers. The performance difference particularly becomes apparent when the coating is applied on human finger nails and tested for durability. UV nail gel coatings can easily last for two weeks or more and still look like new whereas conventional nail polishes are easily scratched and will chip or peel from the natural nail in one to five days. UV nail gels are typically based on acrylates that cure quickly into dense, crosslinked thermoset coatings within half a minute or so. This is an advantage as the coating becomes almost immediately resistant to denting and scratching. Conventional nail lacquers show significant sensitivity to denting while the solvent evaporates from the coating and this requires great care by the individual as the coating dries and hardens; a process that can take easily fifteen to twenty minutes. However, conventional nail polish is easily removed with solvent whereas it can take some effort to remove a fully cured UV nail gel from the nail surface. An expensive UV light also is required for UV nail gel application and this has limited the success of UV nail gels in the mass market for home use. The expense of a UV light is less of an issue for professional salons where a right balance between service rate and a customers' perception of service is more important. As such, there is a need in the consumer market place for durable nail coatings that can cure quickly but do not require procurement of an UV light.

Highly crosslinked, durable coating compositions can be achieved using Michael addition chemistry. The Michael addition reaction involves the nucleophilic addition of a Michael donor, such as a carbanion or another nucleophile to a Michael acceptor, such as an α,β-unsaturated carbonyl. As such, the base catalyzed addition of activated methylene moieties to electron deficient C═C double bonds are known in coatings applications. Representative examples of suitable materials that can provide activated methylene or methine groups are generally disclosed in U.S. Pat. No. 4,871,822, which resins contain a methylene and/or monosubstituted methylene group in the alpha-position to two activating groups such as, for example, carbonyl, cyano, sulfoxide and/or nitro groups. Preferred are resins containing a methylene group in the alpha-position to two carbonyl groups, such as malonate and/or acetoacetate group-containing materials, malonates being most preferred. The α,β-unsaturated carbonyl typically is an acrylate material and representative materials have been disclosed in U.S. Pat. No. 4,602,061. The Michael reaction is fast, can be carried out at ambient temperatures and gives a chemically stable crosslinking bond without forming any reaction by-product.

A typical crosslinkable coating composition comprises a resin ingredient A (Michael donor), a resin ingredient B (Michael acceptor) and a base to start and catalyze the Michael addition reaction. The base catalyst should be strong enough to abstract, i.e. activate a proton from resin ingredient A to form the Michael donor carbanion species. Since the Michael addition cure chemistry can be very fast, the coating formulator is challenged to control the speed of the reaction to achieve an acceptable balance of pot life, open time, tack free time and cure time. Pot life is defined as the amount of time during which the viscosity of a mixed reactive system doubles. Working life or working time informs the user how much time they have to work with a reactive two-part system before it reaches such a high state of viscosity, or other condition, that it cannot be properly worked with to produce an acceptable application result. Gel time is the amount of time it takes for a mixed, reactive resin system to gel or become so highly viscous that it has lost fluidity. The open time of a coating is a practical measure of how much time it takes for a drying or curing coating to reach a stage where it can no longer be touched by brush or roller when applying additional coating material without leaving an indication that the drying or curing coating and newly applied coating did not quite flow together. These indications normally take the form of brush or roller marks and sometimes a noticeable difference in sheen levels. The tack free time is the amount of time it takes for a curing or drying coating to be no longer sticky to the touch, i.e. the time for a system to become hard to the touch, with no tackiness. Cure time is the amount of time it takes for a coating system to reach full final properties.

The Michael reaction starts the very moment when coating resin ingredients A and B are mixed together with a suitable base. Since it is a fast reaction, the material in a mixing pot starts to crosslink and the fluid viscosity starts to rise. This limits the pot life, working time and general use as a coating. A dormant initiator that is essentially passive while coating material remains in a mixing vessel but that activates the Michael addition reaction upon film formation allows for longer pot life and working time, yet would show good open time, tack free time and cure time. Hence, the application of dormant initiator technology can provide the formulator with tools to control the speed of the reaction in order to achieve desirable cure characteristics.

U.S. Pat. No. 8,962,725 describes a blocked base catalyst for Michael addition, which is based on substituted carbonate salts. Preferred Michael donor resins are based on malonate and Michael acceptor resins are acrylates. The substituted carbonates can bear substituents, but these should not substantially interfere with the crosslinking reaction between malonate and acrylate. The carbonate salts release carbon dioxide and a strong base upon activation by means of film formation. The base is either hydroxide or alkoxide. Before practical pot life and gel times are achieved with acceptable curing characteristics, the carbonate requires presence of a certain amount of water in the coating formulation for the blocking of the base to become effective. All disclosed blocked carbonate examples utilize methanol and/or water. However, malonate esters are known to be susceptible to base hydrolysis, particularly when water is present. Hence, the water necessary to block the carbonate base can thus degrade malonate oligomers or polymers at the same time, which in turn can lead to altered coatings performance. The hydrolysis product furthermore can result in undesirable destruction of base catalyst by means of formation of malonate salt; a reaction which is cloaked as longer pot life and gel time. Presence of water can also be quite problematic in certain coatings applications. Wood grain raising is a significant problem when water is present in wood coatings; water penetrates into wood, which causes swelling and lifting of fibers and this leaves a rough surface. Water also can cause flash rust, i.e. appearance of rust spots on a metal surface during drying of newly applied paint that contains water. Longer term rust formation in terms of corrosion may also be a problem when dealing with formulations that contain water.

SUMMARY OF INVENTION

In one embodiment, the present invention provides for a nail polish composition containing a crosslinkable coating composition comprising: ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and a carbonate initiator of Formula (1)

wherein R₇ is selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms; and A^(n+) is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A^(n+) is not an acidic hydrogen; at least one colorant independently selected from the group consisting of (i) a dye; (ii) an inorganic pigment; or an (iii) a lake; and optionally further comprising ammonium carbamate (H₂NR₈R₉+—OC═ONR₈R₉), wherein R₈ R₉ are each independently selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.

In one embodiment, the present invention provides a nail polish composition wherein a dye is selected from the group consisting of D&C Red 21, D&C Red No. 22, D&C Red No. 28, D&C Red No. 30, D&C Red No. 33, D&C Red No. 40, D&C Black No. 2, D&C Yellow No. 5, D&C Green No. 5, Annatto and Caramel. In one such embodiment, the inorganic pigment is selected from the group consisting of red iron oxide; yellow iron oxide; titanium dioxide; brown iron oxide; chromium oxide green; iron blue (ferric ferrocyanide blue); ultramarine blue; ultramarine violet; ultramarine pink; black iron oxide; bismuth oxychloride; aluminum powder; manganese violet; mica; bronze powder; copper powder; guanine and combinations thereof. In another such embodiment, the lake is a D&C lake.

In one embodiment, the present invention provides a nail polish composition wherein ingredient A is selected from the group consisting of compounds, oligomers or polymers. In one such embodiment, ingredient A is independently selected from a malonate group containing compound, a malonate group containing oligomer, a malonate group containing polymer, an acetoacetate group containing compound, an acetoacetate group containing oligomer, an acetoacetate group containing polymer or combinations thereof. In another such embodiment, the malonate group containing compound, malonate group containing oligomer, malonate group containing polymer, an acetoacetate group containing compound, acetoacetate group containing oligomer, or acetoacetate group containing polymer are each selected from the group consisting of: polyurethanes, polyesters, polyacrylates, epoxy polymers, polyamides, polyesteramides or polyvinyl polymers, wherein such compounds, oligomers or polymers have a malonate group or acetoacetate group located in a main chain of such compound or oligomer or polymer or a side chain of such compound or oligomer or polymer.

In one embodiment, the present invention provides a nail polish composition wherein wherein ingredient B is selected from the group consisting of acrylates, fumarates, maleates and combinations thereof. In one such embodiment, the acrylate is independently selected from the group consisting of hexanediol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate bis(2-hydroxyethyl acrylate), trimethylhexyl dicarbamate, bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyl dicarbamate, bis(2-hydroxyethyl acrylate) methylene dicyclohexyl dicarbamate and combinations thereof.

In one embodiment, the present invention provides a nail polish composition wherein ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least two pendant ethylenically unsaturated groups each activated by an electron-withdrawing group.

DETAILED DESCRIPTION

The invention disclosed here is a crosslinkable composition comprising a resin ingredient A (Michael donor), a resin ingredient B (Michael acceptor) and a carbonate initiator ingredient C. The invention generally is useful as a decorative and/or functional coating, and the invention particularly is useful as a coating for human finger nails or toe nails.

Resin Ingredient A (Michael Donor):

Resin ingredients A are compounds, oligomers or polymers that contain functional groups that have reactive protons that can be activated to produce a carbanion Michael donor. In one embodiment, the functional group can be a methylene or methine group and resins have been described in U.S. Pat. No. 4,602,061 and U.S. Pat. No. 8,962,725 for example. In one embodiment, resin ingredients A are those derived from malonic acid or malonate esters, i.e. malonate. Oligomeric or polymeric malonate compounds include polyurethanes, polyesters, polyacrylates, epoxy resins, polyamides, polyesteramides or polyvinyl resins each containing malonate groups, either in the main chain or the side chain or in both.

In one embodiment, polyurethanes having malonate groups may be obtained, for instance, by bringing a polyisocyanate into reaction with a hydroxyl group containing ester or polyester of a polyol and malonic acid/malonates, by esterification or transesterification of a hydroxyfunctional polyurethane with malonic acid and/or a dialkyl malonate. Examples of polyisocyanates include hexamethylenediisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and addition products of a polyol with a diisocyanate, such as that of trimethylolpropane to hexamethylene diisocyanate. In one embodiment, the polyisocyanate is selected from isophorone diisocyanate and trimethyhexamethylene diisocyanate. In another embodiment, the polyisocyanate is isophorone diisocyanate. In some embodiments, hydroxyfunctional polyurethanes include the addition products of a polyisocyanate, such as the foregoing polyisocyanates, with di- or polyvalent hydroxy compounds, including diethyleneglycol, neopentyl glycol, dimethylol cyclohexane, trimethylolpropane, 1,3-propandiol, 1,4-butanediol, 1,6-hexanediol and polyether polyols, polyester polyols or polyacrylate polyols. In some embodiments, the di- or polyvalent hydroxy compounds include diethyleneglycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. In other embodiments, the di- or polyvalent hydroxy compounds include diethyleneglycol and 1,6-hexanediol.

In one embodiment, malonic polyesters may be obtained, for instance, by polycondensation of malonic acid, an alkylmalonic acid, such as ethylmalonic acid, a mono- or dialkyl ester of such a carboxylic acid, or the reaction product of a malonic ester and an alkylacrylate or methacrylate, optionally mixed with other di- or polycarboxylic with one or more dihydroxy and/or polyhydroxy compounds, in combination or not with mono hydroxy compounds and/or carboxyl compounds. In some embodiments, polyhydroxy compounds include compounds containing 2-6 hydroxyl group and 2-20 carbon atoms, such as ethylene glycol, diethyleneglycol, propylene glycol, trimethylol ethane, trimethylolpropane, glycerol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, 1,12-dodecanediol and sorbitol. In some embodiments, the polyhydroxyl compounds include diethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol. In other embodiments, the polyhydroxyl compounds include propylene glycol and 1,6-hexanediol. In certain embodiments, the polyhydroxy may be a primary alcohol and in certain other embodiments, the polyhydroxy may be a secondary alcohol. Examples of polyols with secondary alcohol groups are 2,3-butanediol, 2,4-pentanediol and 2,5-hexanediol and the like.

In one embodiment, malonate group-containing polymers also may be prepared by transesterification of an excess of dialkyl malonate with a hydroxy functional polymer, such as a vinyl alcohol-styrene copolymer. In this way, polymers with malonate groups in the side chains are formed. After the reaction, the excess of dialkyl malonate may optionally be removed under reduced pressure or be used as reactive solvent.

In one embodiment, malonate group or acetoacetate group containing polymers may also be obtained from reaction with malonate or acetoacetonate with polyols, such as those polyols that are commercially sold for reaction with isocyanates to form polyurethane coatings.

In one embodiment, malonic epoxy esters may be prepared by esterifying an epoxy polymer with malonic acid or a malonic monoester, or by transesterifying with a dialkylmalonate, optionally in the presence of one or more other carboxylic acids or derivatives thereof.

In one embodiment, polyamides having malonate groups may be obtained in the same manner as polyesters, at least part of the hydroxy compound(s) being replaced with a mono- or polyvalent primary and/or secondary amine, such as cyclohexylamine, ethylene diamine, isophorone diamine, hexamethylene diamine, or diethylene triamine.

In some embodiments, such polyamide compounds can be obtained when 12-hydroxystearic acid is reacted with a diamine such as ethylenediamine. Such polyamides have secondary alcohol groups, which can be esterified with malonic acid or malonate in a second reaction step. In some embodiments, other diamines may also be used in the reaction with 12-hydroxystearic acid, for example: xylylenediamine, butylenediamine, hexamethylenediamine, dodecamethylenediamine, and even dimer amine, which is derived from dimer acid. Polyamines may also be used, but in a right stoichiometric ratio as to avoid gelling of the polyamide in the reactor. Lesquerolic acid may also be used in reactions with polyamines to yield polyamides bearing secondary alcohol groups, which can be used in reactions with malonate to form malonate containing compounds. Reactions that yield malonamides are much less desirable.

In some embodiments, the above mentioned malonate resins may be blended together to achieve optimized coatings properties. Such blends can be mixtures of malonate modified polyurethanes, polyesters, polyacrylates, epoxy resins, polyamides, polyesteramides and the like, but mixtures can also be prepared by blending various malonate modified polyesters together. In some other embodiments, various malonate modified polyurethanes can be mixed together, or various malonate modified polyacrylates, or malonate modified epoxy resins, or various malonate modified polyamides, malonate modified polyesteramides.

In certain embodiments, malonate resins are malonate group containing oligomeric esters, polyesters, polyurethanes, or epoxy esters having 1-100, or 2-20 malonate groups per molecule. In some such embodiments, the malonate resins should have a number average molecular weight in the range of from 250 to 10,000 and an acid number not higher than 5, or not higher than 2. Use may optionally be made of malonate compounds in which the malonic acid structural unit is cyclized by formaldehyde, acetaldehyde, acetone or cyclohexanone. In some embodiments, molecular weight control may be achieved by the use of end capping agents, typically monofunctional alcohol, monocarboxylic acid or esters. In one embodiment, malonate compounds may be end capped with one or more of 1-hexanol, 1-octanol, 1-dodecanol, hexanoic acid or its ester, octanoic acid or its esters, dodecanoic acid or its esters, diethyleneglycol monoethyl ether, trimethylhexanol, and t-butyl acetoacetate, ethyl acetoacetate. In one such embodiment, the malonate is end capped with 1-octanol, diethyleneglycol monoethyl ether, trimethylhexanol, t-butyl acetoacetate and ethyl acetoacetate. In another such embodiment, the malonate is end capped t-butyl acetoacetate, ethyl acetoacetate and combinations thereof.

Monomeric malonates may optionally be used as reactive diluents, but certain performance requirements may necessitate removal of monomeric malonates from resin ingredient A.

In some embodiments, resin ingredients A include oligomeric and/or polymeric acetoacetate group-containing resins. In some embodiments, such acetoacetate group-containing resins are acetoacetic esters as disclosed in U.S. Pat. No. 2,759,913, diacetoacetate resins as disclosed in U.S. Pat. No. 4,217,396 and acetoacetate group-containing oligomeric and polymeric resins as disclosed in U.S. Pat. No. 4,408,018. In some embodiments, acetoacetate group-containing oligomeric and polymeric resins can be obtained, for example, from polyalcohols and/or hydroxy-functional polyether, polyester, polyacrylate, vinyl and epoxy oligomers and polymers by reaction with diketene or transesterication with an alkyl acetoacetate. Such resins may also be obtained by copolymerization of an acetoacetate functional (meth)acrylic monomer with other vinyl- and/or acrylic-functional monomers. In certain other embodiments, the acetoacetate group-containing resins for use with the present invention are the acetoacetate group-containing oligomers and polymers containing at least 1, or 2-10, acetoacetate groups. In some such embodiments, such acetoacetate group containing resins should have Mn in the range of from about 100 to about 5000 g/mol, and an acid number of about 2 or less. Resins containing both malonate and acetoacetate groups in the same molecule may also be used.

In another embodiment, the above mentioned malonate group containing resins and acetoacetate group-containing resins may also be blended to optimize coatings properties as desired, often determined by the intended end application.

Structural changes at the acidic site of malonate or acetoacetate can alter the acidity of these materials and derivatives thereof. For instance, pKa measurements in DMSO show that diethyl methylmalonate (MeCH(CO₂Et)₂) has a pKa of 18.7 and diethyl ethylmalonate (EtCH(CO₂Et)₂) has a pKa of 19.1 whereas diethyl malonate (CH₂(CO₂Et)₂) has a pKa of 16.4. Resin ingredient A may contain such substituted moieties and therewith show changes in gel time, open time, cure time and the like. For example, resin ingredient A may be a polyester derived from a polyol, diethyl malonate and diethyl ethylmalonate.

Resin Ingredient B (Michael Acceptor):

Resin ingredients B (Michael acceptor) generally can be materials with ethylenically unsaturated moieties in which the carbon-carbon double bond is activated by an electron-withdrawing group, e.g. a carbonyl group in the alpha-position. In some embodiments, resin ingredients B are described in: U.S. Pat. No. 2,759,913, U.S. Pat. No. 4,871,822, U.S. Pat. No. 4,602,061, U.S. Pat. No. 4,408,018, U.S. Pat. No. 4,217,396 and U.S. Pat. No. 8,962,725. In certain embodiments, resin ingredients B include acrylates, fumarates and maleates.

In some embodiments, resin ingredients B are the acrylic esters of chemicals containing 2-6 hydroxyl groups and 2-20 carbon atoms. These esters may optionally contain hydroxyl groups. In some such embodiments, examples of such acrylic esters include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate. In one such embodiment, acrylic esters include trimethylolpropane triacrylate, di-trimethylolproane tetraacrylate, dipentaerythritol hexaacrylate, pentaerythritol ethoxylated (EO)_(n) tetraacrylate, trimethylolpropane ethoxylated(EO)_(n) triacrylate and combinations thereof. In another embodiment, acrylamides may be used as a resin ingredient B.

In other embodiments, resin ingredients B are polyesters based upon maleic, fumaric and/or itaconic acid (and maleic and itaconic anhydride), and chemicals with di- or polyvalent hydroxyl groups, optionally including materials with a monovalent hydroxyl and/or carboxyl functionality.

In other embodiments, resin ingredients B are resins such as polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least two pendant ethylenically unsaturated groups each activated by an electron-withdrawing group. These include, for example, urethane acrylates obtained by reaction of a polyisocyanate with an hydroxyl group-containing acrylic ester, e.g., an hydroxyalkyl ester of acrylic acid or a resins prepared by esterification of a polyhydroxyl material with acrylic acid; polyether acrylates obtained by esterification of an hydroxyl group-containing polyether with acrylic acid; polyfunctional acrylates obtained by reaction of an hydroxyalkyl acrylate with a polycarboxylic acid and/or a polyamino resin; polyacrylates obtained by reaction of acrylic acid with an epoxy resin; and polyalkylmaleates obtained by reaction of a monoalkylmaleate ester with an epoxy polymer and/or an hydroxy functional oligomer or polymer. In certain embodiments, polyurethane acrylate resins may be prepared by reaction of hydroxyalkyl acrylate with polyisocyanate. Such polyurethane acrylate resins independently include bis(2-hydroxyethyl acrylate) trimethylhexyl dicarbamate [2-hydroxyethyl acrylate trimethylhexamethylene diisocyanate (TMDI) adduct], bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyl dicarbamate [2-hydroxyethyl acrylate 1,3,3-trimethylcyclohexyl diisocyanate/isophorone diisocyanate (IPDI) adduct], bis(2-hydroxyethyl acrylate) hexyl dicarbamate [2-hydroxyethyl acrylate hexamethylene diisocyanate (HDI) adduct], bis(2-hydroxyethyl acrylate) methylene dicyclohexyl dicarbamate [2-hydroxyethyl acrylate methylene dicyclohexyl diisocyanate (HMDI) adduct], bis(2-hydroxylethyl acrylate) methylenediphenyl dicarbamate [2-hydroxyethyl acrylate methylenediphenyl diisocyanate (MDI) adduct], bis(4-hydroxybutyl acrylate) 1,3,3-trimethylcyclohexyl dicarbamate [4-hydroxybutyl acrylate IPDI adduct], bis(4-hydroxybutyl acrylate) trimethylhexyl dicarbamate [4-hydroxybutyl acrylate TMDI adduct], bis(4-hydroxybutyl acrylate) hexyl dicarbamate [4-hydroxybutyl acrylate HDI adduct], bis(4-hydroxybutyl acrylate) methylene dicyclohexyl dicarbamate [4-hydroxybutyl acrylate HMDI adduct], bis(4-hydroxybutyl acrylate) methylenediphenyl dicarbamate [4-hydroxybutyl acrylate MDI adduct].

In other embodiments, resin ingredients B have unsaturated acryloyl functional groups. In other certain embodiments, resin ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least one pendant acryloyl functional group.

In certain embodiments, the acid value of the activated unsaturated group-containing material (resin ingredient B) is sufficiently low to not substantially impair the Michael addition reaction, for example less than about 2, and further for example less than 1 mg KOH/g.

As exemplified by the previously incorporated references, these and other activated unsaturated group containing resins, and their methods of production, are generally known to those skilled in the art, and need no further explanation here. In certain embodiments, the number of reactive unsaturated group ranges from 2 to 20, the equivalent molecular weight (EQW: average molecular weight per reactive functional group) ranges from 100 to 2000, and the number average molecular weight Mn ranges from 100 to 5000.

In one embodiment, the reactive part of resin ingredients A and B can also be combined in one A-B type molecule. In this embodiment of the crosslinkable composition both the methylene and/or methine features as well as the α,β-unsaturated carbonyl are present in the same molecule, be it a monomer, oligomer or polymer. Mixtures of such A-B type molecules with ingredient A and B are also useful.

Each of the foregoing embodiments of resin ingredient A and resin ingredient B may be combined with the various embodiments of a dormant carbonate initiator ingredient C, described below, to arrive at the inventions described herein. In one embodiment, resin ingredient A is a polyester malonate composition and resin ingredient B is a polyester acrylate. In another embodiment, resin ingredient A is a polyurethane malonate composition and resin ingredient B is a polyester acrylate. In another embodiment, resin ingredient A is a polyurethane malonate composition and resin ingredient B is a polyester acrylate. In another embodiment, resin ingredient A is a polyurethane malonate composition and resin ingredient B is a polyurethane acrylate. In another embodiment, resin ingredient A is a polyester malonate having acetoacetate end groups and resin ingredient B is a polyester acrylate. In yet another embodiment, resin ingredient A is a polyester malonate having acetoacetate end groups and resin ingredient B is a polyurethane acrylate. In still yet another embodiment, resin ingredient A is a polyester malonate having acetoacetate end groups and resin ingredient B is a mixture of polyester acrylate and polyurethane acrylate.

In the foregoing embodiments, the number of reactive protons for resin ingredients A, and the number of α,β-unsaturated carbonyl moieties on resin ingredient B can be utilized to express desirable ratios and ranges for resin ingredients A and B. Typically, the mole ratio of reactive protons of ingredient A that can be activated with subsequent carbanion formation relative to the activated unsaturated groups on ingredient B is in the range between 10/1 and 0.1/1, or between 4/1 and 0.25/1, or between 3.3/1 and 0.67/1. However, the optimal amount strongly depends also on the number of reactive groups present on ingredients A and/or B.

The amount of dormant carbonate initiator used, expressed as mole ratio of protons that can be abstracted to form an activated Michael donor species (e.g. the methylene group of malonate can provide two protons for reactions, while a methine group can provide one proton to form an activated species) relative to initiator, ranges from about 1000/1 to 1/1, or from 250/1 to 10/1, or from 125/1 to 20/1 but the optimal amount to be used depends also on the amount of solvent present, reactivity of various acidic protons present on resin ingredients A and/or B.

Carbonate Initiator Ingredient C:

Ingredient C may be a carbonate initiator having a structure as shown in Formula 1:

R₇ can be independently selected and is hydrogen or a linear or branched alkyl group with 1 to 22 carbon atoms; 1 to 8 carbon atoms; or 1 to 3 carbon atoms. In some such embodiments, R₇ is an unsubstituted alkyl group. In other such embodiments, R₇ is a substituted alkyl group including hydroxyl substituted alkyl groups. In some embodiments, R₇ is independently selected from a methyl group, an ethyl group, a propyl group, or a butyl group. For the foregoing embodiments, A^(n+) is a cationic material and n is an integer equal or greater than 1; A^(+n) is not an acidic hydrogen. In some embodiments, A^(n+) can be a monovalent cation, such as an alkali metal, earth alkali metal or another monovalent metal cation, a quaternary ammonium or a phosphonium compound. In some embodiments, A^(n+) can also be a multivalent metal cation, or a compound bearing more than one quaternary ammonium or phosphonium groups, or can be a cationic polymer. In certain embodiments, A^(n+) is a monovalent quaternary ammonium compound where n is 1. A^(n+) cannot have acidic protons that can protonate the carbanion Michael donor derived from resin ingredient A.

In a certain embodiment, A^(n+) of formula 1 is a monovalent quaternary ammonium compound and as shown in formula 2. A large selection of such quaternary ammonium compounds is commercially available from various manufacturers. In one embodiment, quaternary ammonium compounds are derived from tertiary amines and quaternized with a methyl or benzyl group. In other embodiments, tetra alkyl ammonium compounds also can be used. R3, R4 and R5 are independently selected and are linear or branched alkyl chains having from 1 to 22 carbon atoms; or 1 to 8 carbon atoms. In such foregoing embodiments, R6 is selected from a methyl or a benzyl group or an alkyl group having from 2 to 6 carbon atoms. Such quaternary ammonium compounds are commercially available as salts and the anion typically is chloride, bromide, methyl sulfate, or hydroxide. Quaternary ammonium compounds with methylcarbonate or ethylcarbonate anions are also available.

Examples of A^(n+) of formula 1 include dim ethyl diethylammonium, dimethyldipropylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, tripentylmethylammonium, trihexylmethylammonium tetraethylammonium, tetrapropylammonium, tetrabutyl ammonium, tetrapentylammonium, tetrahexylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium, benzyltributylammonium, benzyltripentyammonium, and benzyltrihexylammonium.

The crosslinkable composition of this invention preferably contains some solvent. The coating formulator may choose to use an alcohol, or a combination of alcohols as solvent for a variety of reasons. Other solvents like ethylacetate or butylacetate may also be used, potentially in combination with alcohol solvents. Ethanol is a preferred solvent. Isopropyl alcohol also is a preferred solvent. Methanol is not preferred as a solvent because of health and safety risks, and is particularly not preferred and cannot be used when the crosslinkable composition is used as a coating for finger nails and toe nails. Other oxygenated, polar solvents such as ester or ketones for instance, are also suitable and can be used, potentially in combination with alcohol. Other organic solvents may also be used.

In some embodiments of the crosslinkable composition, water may be added to the composition. further comprising water concentration selected from the group consisting of less than 10 wt. %, less than 5 wt. %; less than 1 wt. %; less than 0.1 wt. %; less than 0.01 wt. % water.

Some embodiments of the crosslinkable composition of this invention may also be formulated without solvent in some cases. In other embodiments, the crosslinkable coating contains typically at least 5 wt % of solvent, preferably between 5% and 45%, more preferable between 5% and 35%, but preferable not more than 60% because of VOC restrictions. In such embodiments, the organic solvent is independently selected from the group consisting of an alcohol, ester, ether, glycol ether, ketone, aromatic and combinations thereof. In certain embodiments the alcohol is independently selected from the group consisting of methanol, ethanol, iso-propanol, butanol, iso-butanol, t-butanol and combinations thereof.

The crosslinkable composition useful as a coating can be formulated as a one component, a two component system or a three component system. In an embodiment of a two component system, initiator ingredient C is added to a mixture of ingredients A and B just prior to use; ingredient D may optionally be added to the initiator ingredient C or the mixture of ingredients A and B. In an alternative embodiment, ingredients A and C are mixed, and ingredient B is added prior to use ingredient; D may optionally be added to the mixture of ingredient A and initiator ingredient C or ingredient B. In yet another embodiment, ingredient A is added to a mixture of ingredients B and C prior to use; ingredient D may optionally be added to ingredient A or the mixture of ingredient B and initiator C. In certain embodiments, pot life, working time and gel time can be adjusted by selection of the initiator structure, the amount used in the crosslinkable composition, presence of additional ammonium carbamate and to a certain extent the amount of solvent and/or water. A gel time of hours, and even days can be readily achieved, and gel times of weeks are possible. As such, the dormant initiator allows for an opportunity to formulate a three component paint system. In such embodiment of a one component system, ingredients A, B, C and D are mixed together, optionally with other ingredients to formulate a paint, which is then canned and stored until use. In certain embodiments, a one component system can be enhanced by means of using excess carbon dioxide gas over the crosslinkable composition as to further improve pot life and gel time. For instance, a paint composition formulated according to the invention may have a protective atmosphere of carbon dioxide over the paint volume; and in yet another embodiment, a container containing the crosslinkable composition may even be pressurized with carbon dioxide. In another embodiment, a one component system containing ingredients A, B and C are in a container filled to capacity with essentially no space remaining for other solids, liquid or gaseous ingredients and optionally containing ammonium carbamate. In yet another embodiment, additional ammonium carbamate may further enhance stability in such one component coating formulations.

In another embodiment, the present invention provides for the crosslinkable coating composition wherein ingredient A, ingredient B and the carbonate initiator are contained in a container having two or more chambers, which are separated from one another. In one such embodiment, ingredient A and ingredient B are contained in separate chambers to inhibit any reaction. In another such embodiment, the carbonate initiator is contained in the chamber having ingredient A, and optionally containing CO₂ and/or ammonium carbamate. In another such embodiment, the carbonate initiator is contained in the chamber having ingredient B, and optionally containing CO₂ and/or ammonium carbamate.

In another embodiment, the present invention provides for the crosslinkable coating composition such that ingredient A and ingredient B are contained in the same chamber and the carbonate initiator is contained in a separate chamber to inhibit any reaction and said separate chamber optionally containing CO₂ and/or ammonium carbamate.

Malonate esters are known to be susceptible to base hydrolysis, particularly when water is present. Water potentially can lead to undesirable destruction of initiator by means of formation of malonate salt and it can degrade malonate oligomers or polymers, which in turn can lead to altered coatings performance. Transesterification reactions also can occur with malonate esters and alcohol solvent. These reactions potentially can be limiting to the formulation of an acceptable working life, as a coatings formulator seeks to increase pot life and gel time for a crosslinkable composition formulated either as a one or two component system. However, primary alcohols such as methanol and ethanol are much more active in transesterification reactions than secondary alcohols such as isopropanol, while tertiary alcohols are generally least active. Furthermore, additional resistance towards hydrolysis and transesterification can be obtained when malonate polyester resins are derived from malonic acid, or a dialkylmalonate such as diethylmalonate, and polyols bearing secondary alcohol groups; such as 2,3-butanediol, 2,4-pentanediol and 2,5-hexanediol and the like. The combination of such polyester resins and non-primary alcohol solvents, such as isopropanol or butanol, is particularly useful in achieving desirable resistance towards transesterification reactions. In a preferred approach, resin ingredient A comprises malonate moieties that have been esterified with polyols bearing secondary alcohol groups and where secondary alcohol is present as solvent in the crosslinkable composition of this invention. In yet another approach, tertiary alcohols are used as solvent or solvents as used that do not participate in transesterification reactions. Other resins may also be formulated using such stabilizing approaches towards resin breakdown and such approaches are well known to one skilled in the art and need not be further described here.

The number of reactive protons for ingredients A, and the number of α,β-unsaturated carbonyl moieties on resin ingredient B can be utilized to express desirable ratio's and ranges for ingredients A and B. Typically, the mole ratio of reactive protons of ingredient A that can be activated with subsequent carbanion formation relative to the activated unsaturated groups on ingredient B is in the range between 10/1 and 0.1/1, preferably between 4/1 and 0.25/1, and more preferably 3.3/1 and 0.67/1. However, the optimal amount strongly depends also on the number of such active functionalities present on ingredients A and/or B. Although good tack free time may be obtained over a wide ratio range, coatings properties, such as hardness for instance may show a smaller preference range.

The crosslinkable composition of this invention comprising ingredients A, B and C may optionally contain an additional ingredient D, which once activated, can react with the Michael acceptor. Ingredient D has one or more reactive protons that are more reactive, i.e. more acidic than those of ingredient A (the pKa of ingredient D is lower than that of ingredient A). The reactive protons of ingredient D are present at a fraction based on the reactive protons of ingredient A. The fraction ranges from 0 to 0.5, more preferably from 0 to 0.35, even more preferable between 0 and 0.15.

Examples of ingredient D include; succinimide, isatine, ethosuximide, phthalimide, 4-nitro-2-methylimidazole, 5,5-dimethylhydantioin, phenol, 1,2,4-triazole, ethylacetoacetate, 1,2,3-triazole, ethyl cyanoacetate, benzotriazole, acetylacetone, benzenesulfonamide, 1,3-cyclohexanedione, nitromethane, nitroethane, 2-nitropropane, diethylmalonate, 1,2,3-triazole-4,5-dicarboxylic acid ethyl ester, 1,2,4-triazole-3-carboxylic acid ethyl ester, 3-Amino-1,2,4-triazole, 1H-1,2,3-triazole-5-carboxylic acid ethyl ester, 1H-[1,2,3]triazole-4-carbaldehyde, morpholine, purines such as purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid and isoguanine; pyrimidines, such as thymine and cytosine; uracil, glycine, ethanimidamide, cysteamine, allantoin, N,N-dimethylglycine, allopurinol, N-methylpyrrolidine, benzeneboronic acid, salicyl aldehyde, 3-hydroxybenzaldehyde, 1-naphthol, methylphenidate and Vitamin E.

In other embodiments, ingredient D may be incorporated into resin ingredient A. In such embodiments, substituted succinimides, including hydroxyl group containing succinimide derivatives, 3-hydroxy-2,5-pyrrolidinedione and 3-(hydroxymethyl)-2,5-pyrrolidinedione, or carboxylic acid group containing succinimide derivative, 2,5-dioxo-3-pyrrolidinecarboxylic acid can undergo condensation reactions with either acid/ester groups or hydroxyl groups at the end of resin A polymer chain, where the succinimide moiety will be incorporated into the polymer backbone as end cap.

The amount of carbonate initiator used, expressed as mole ratio of protons that can be abstracted to form an activated Michael donor species (e.g. the methylene group of malonate can provide two protons for reactions, while a methine group can provide one proton to form an activated species) relative to initiator, ranges from about 1000/1 to 1/1, more preferably from 250/1 to 10/1, even more preferable from 125/1 to 20/1 but the optimal amount to be used depends also on the amount of solvent present, reactivity of various acidic protons present on ingredient A and, if present, ingredient D, on pigments or dyes present in the system, on the number of active functionalities present on ingredients A and/or B and the like. Hence, the optimal amount needs to be determined experimentally to arrive at preferred curing characteristics.

The crosslinkable coating composition of this invention can comprise one or more pigments, dyes, effect pigments, phosphorescent pigments, flakes and fillers. Metal flake effect pigments may also be used in the crosslinkable coating composition of this invention and this is an advantage over UV curable nail gel coatings as the UV cure process is hindered by such pigments and these metal flakes are therefore typically not used in such long lasting nail coatings. The cross-linkable coating composition of this invention can comprise other Michael addition reactive and non-reactive resins or polymers, for instance to facilitate adhesion, and/or aid in coating removal. Such removal aids may be solvent-dissolvable compounds, resins, oligomers or polymers, which are dispersed in the polymerized structure and can be easily dissolved by a solvent to facilitate solvent absorption and migration during removal of the coating.

The crosslinkable coating compositions of this invention may contain one or more of FD&C or D&C dyes, pigments and/or lakes. Lakes are colorants where one or more of the FD&C or D&C dyes are adsorbed on a substratum, such as alumina, blanc fixe, gloss white, clay, titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate or calcium carbonate. In certain embodiments, the D&C dye is independently selected from D&C Red 21, D&C Red No. 22, D&C Red No. 28, D&C Red No. 30, D&C Red No. 40, D&C Red No. 33, D&C Black No. 2, D&C Yellow No. 5, D&C Green No. 5, Annatto, Caramel and combinations thereof. In certain embodiments, the inorganic pigment is selected from the group consisting of red iron oxide; yellow iron oxide; titanium dioxide; brown iron oxide; chromium oxide green; iron blue (ferric ferrocyanide blue); ultramarine blue; ultramarine violet; ultramarine pink; black iron oxide; bismuth oxychloride; aluminum powder; manganese violet; mica; bronze powder; copper powder; guanine and combinations thereof.

Certain embodiments of the formulation may optionally comprise resins, such as, but not limited to nitrocellulose, polyvinylbutyral, tosylamide formaldehyde and/or tosylamide expoxy resins. Certain other embodiments, the crosslinkable coating compositions may comprise a cellulose acetate alkylate selected from the group consisting of cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof.

Such resins may act as film formers, adhesion promoters, and aids to removal. These resins may also qualify as solvent-dissolvable resins.

The cross-linkable coating composition of this invention can comprise additives such as wetting agents, defoamers, rheological control agents, ultraviolet (UV) light stabilizers, dispersing agents, flow and leveling agents, optical brighteners, gloss additives, radical inhibitors, radical initiators, adhesions promotors, gloss additives, radical inhibitors, radical initiators, plasticizers and combinations thereof. The selection of these materials and additives will, of course, depend on the intended use of the coating composition. However, all these materials need to be carefully screened as some of these may react with the carbonate initiator and therefore are not suitable for use in the crosslinkable composition should such a reaction occur and significantly interfere with the curing process. The above described materials and additives are commonly used in the coatings industry and are well known to one skilled in the art and need not be further described here.

In certain embodiments, the crosslinkable composition of this invention formulated as a nail polish may be packaged in a single unit package good for one time use. Such single serve units contain enough coating material to decorate all finger and toe nails. A single use package may contain a nail polish formulated as a one component system where all ingredients are mixed in one chamber, potentially with extra ammonium carbamate and carbon dioxide to push back on the dormant carbonate initiator in one chamber filled to capacity with essentially no space remaining for other solid, liquid or gaseous ingredients. The single unit package may contain more than one chambers when the nail polish system is formulated as a multi component system, e.g. two chambers when the nail polish is formulated as a two component system, or three chambers when ingredients A, B and C are all kept separate until use. Packages are known where a seal between chambers is broken to allow for materials to be mixed in the merged chambers and a proper ratio of components is maintained by virtue of the design of the package. Flexible packages and more rigid containers such as bottles that have more than one chamber where contents can be mixed upon demand are known and are readily available. Single unit packages may also include a brush for application. In another approach deviating from a single use concept, material may be dispensed from a single chamber (flexible) package that can be resealed. Multi chamber package that utilize plungers are also known and proper mixing of components can be insured by use of a mixing nozzle for instance. Material may be dispensed multiple times provided the time between uses does not exceed the working life of the nail polish in a mixing chamber or if the working life is to be exceeded, the mixing nozzle is removed and the package capped and stored until future use when a new mixing nozzle will be used. Many packaging solutions are available from packaging providers and these are well known to one skilled in the art.

In certain embodiments, the cross-linkable coating composition of this invention is particularly useful to decorate finger and toe nails, and can be applied as a three coat nail polish system, with a base coat applied directly on top of the base nail surface, followed by a color coat and finished with a glossy top coat. In another preferred approach, the nail polish system is formulated as a two coat system, where a color coat is applied directly on the bare nail surface, and finished with a glossy top coat, but in yet another approach, and base coat is applied to the nail surface to provide adhesion for a glossy color coat. Another particularly useful approach to decorate nails is where the cross-linkable coating composition of this invention is used as a single coat system, which has good adhesion to the nail surface, color and gloss all in a one coat system. It is understood that multiple coats can be applied over a same coat for any of these one, two or three coat systems.

The following examples further describe and demonstrate illustrative embodiments within the scope of the present invention. The examples are given solely for illustration and are not to be construed as limitations of this invention as many variations are possible without departing from the spirit and scope thereof.

Coating Testing

Tack free time was evaluated by lightly pressing a gloved index finger periodically onto the coating. The time when visible marks in the film are no longer left by the pressed finger, was then recorded as the tack free time.

Gel time was taken as the amount of time it takes for a mixed, reactive resin system to gel or become so highly viscous that it has lost fluidity. Typically, the various ingredients were charged into a 4 ml vial and closed with headspace volume as constant as possible to allow for comparison and the sample was kept at room temperature and tilted at regular time intervals to determine whether the material still flows. If no flow is observed during tiling, the vial was held upside down and if no further flow occurs the materials is gelled.

Fineness of Grind was evaluated with a Hegman Gauge according to the ASTM D1210 test method.

Example 1

General Synthesis of Carbonate Catalyst from Diethylcarbonate.

Most of the methanol solvent from a 40 g tetrabutylammonium hydroxide (TBA OH) solution in methanol (1 M) was removed with a rotary evaporator. The material was not allowed to become completely dry without solvent as dry quaternary ammonium hydroxide base is susceptible to decomposition. Next, 40 grams of ethanol was added and most of the solvent was again removed. This procedure was repeated at least two more times until the methanol effectively had been replaced as determined by NMR. The solution strength is determined by titration (typically 1.7 mmol base/g solution). Next, a precise amount of the TBA OH in solution was mixed with diethyl carbonate (DEtC) in a 1:5 molar ratio respectively and stirred for 1 hour at room temperature using magnetic stirrer. The final clear initiator solution was analyzed by means of titration and NMR. In a similar manner, clear solutions were obtained in 1-propanol and 2-propanol. A solution made using the TBA OH base in methanol resulted in white precipitate which is removed by centrifuge followed by filtration using 0.45μ syringe filter. Transesterification reaction products were observed in the NMR for all cases where the carbonate alkyl group was different from the solvent, e.g. ethanol formation was observed when DEtC was added to TBA OH in isopropanol and isopropyl groups associated with carbonates were also observed.

Example 2 Malonate Resin (I) Synthesis.

A 500 ml reactor was charged with 149.8 g of Polyethylene glycol (PEG 300), 100 g of diethyl malonate (DEM), 32.5 g of 1-octanol and 4-5 drops of titanium (IV) butoxide. The reactor was equipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flow and heating equipment. The mixture was heated to about 180° C. with stirring under nitrogen atmosphere. During an eight-hour reaction time, about 70 ml of ethanol was collected. The final product was a lightly yellow colored liquid with less than 0.15 wt. % of residual DEM as determined by gas chromatography (GC). Gel permeation chromatography (GPC) analysis showed Mw/Mn (PDI) of 4191/2818 (1.49) in gram/mole and a malonate methylene equivalent molecular weight of 360 g/mole.

Example 3 Basic Nail Color Formulation

FD&C and D&C dyes commonly used in nail enamel formulations were evaluated in Michael addition based crosslinkable compositions. Such colorants may also be used in other coating application industries such as automotive and industrial paints, architectural paints, plastics, adhesives and others. Concentrated dispersions of dye in Malonate resin from example 2 were prepared first. Said dispersions were then used to formulate simple nail enamel color coat formulations. All nail enamel color coats were formulated to contain dye concentrations at 3% dye loading by weight. Finally, nail enamel coatings of controlled thickness are prepared to evaluate certain applications and color properties. The following is an example how a dye dispersion and color nail enamel coat is prepared and serves as general preparative example:

Dye Dispersion:

First, 10.04 g of Malonate resin (I) from example 2 was weighed directly into a tared 60 ml capacity mortar and 3.00 g of D&C Red 30 Indigoid dye was weighed in next. A spatula was briefly used to hand blend the dye into the resin and a pestle was then used to grind the paste in the mortar to a fine consistency. The mixture was ground/milled by hand for approximately 10-25 minutes using the pestle and mortar until a Hegman Fineness of Grind value of 7 was achieved. The pigment dispersion was then transferred to a glass jar and sealed for later use.

Nail Enamel Color Coat:

Into a 20 ml glass vial, 0.65 g of the above D&C Red 30 dye dispersion was added. An additional 1.95 g of Malonate resin (I) from example 2 was charged to the vial and 1.58 g of DTMPTA was added next. The materials in the vial were mixed by hand using a spatula to achieve homogeneity. After this, 0.41 g of butylacetate (BA) was mixed in as well. The vial was sealed and vigorously shaken until homogenous. Test panels to be coated were placed into position at this point. Bird Bars (3 & 6 mil) for coating application were made ready. The glass vial was unsealed and 0.41 g of the methanol based catalyst of example 1 was added. The lid was placed back on the vial. The complete mixture was vigorously shaken for 1-3 minutes to make it homogenous. Once mixing was completed, the mixture was promptly cast as films using the Bird Bars on 4″×6″ polycarbonate panels. Tack free time was recorded and coating surface wrinkling was observed as the films cured. Nail enamel coatings typically are about 1.0-1.5 mil thick, sometimes up to 2 mil thick per coating layer when applied by brush on finger- and/or toe nails although even thicker coatings are applied by consumers that are less experienced.

Various dyes were thus evaluated and compared to a dye free (uncolored) control and results are shown in Table 1.

The uncolored nail coating used as a reference film exhibits slight surface wrinkling without any dye present. The amount of surface wrinkling is inherent in the resin/formula combination used for this evaluation. Any worsening of this surface wrinkling is considered less desirable.

The films prepared at 3% dye concentration and 3 mil film wet applied film thickness, were additionally evaluated by color spectrophotometry to monitor color change upon aging. Once the applied coating became tack free, a timer was started. Color measurements were carried out for each film. Each coated panel was measured at 3 different points during the aging process: (1) 1 hr.; (2) overnight (>16 hours); and (3) after 1 week. Color analyses were performed using a calibrated DataColor 800 Spectrophotometer to measure the coated panels. The panels sat in ambient laboratory conditions during the period of aging. The color measurement changes (CIELAB system, L*(0=Black,100=White), a*(+Red,−Green), b*(+Yellow,−Blue), total color change ΔE,) for overnight and 1 week of aging, were determined using the 1 hr. color measurement as the reference point from which the instrument's software calculated the delta values. Whether a color change is noticeable to the eye is a matter of personal opinion for end users of nail color cosmetics. For purposes of this example, color changes of ΔE of <=1.0 were interpreted as Good. Color change of ΔE>1.0 but<=2.0 were interpreted as Fair yet still considered acceptable as being viewed that such a color change would be likely detected by a trained eye only. Color changes of ΔE>2.0 were less desirable as this color change is likely to be readily noticeable even to an untrained eye. A color change ΔE>4.0 is significant, while a color change of ΔE>5 is an entirely different color. The results are shown in Table 2.

TABLE 1 Films - 3 Films - 6 mils applied Thickness mils applied Thickness Tack free Coating Tack free Coating Dye used, time, Surface time, Surface Dye name Wt. % [min] Wrinkling [min] Wrinkling Blank no dye 1.7 slight 2.0 slight Control FD&C 3% 5.3 slight 22.0 moderate Yellow 5 D&C 3% 4.5 none 5.3 none Red 30

TABLE 2 3 mil Wet Film Same Day Color Overnight Cured Analysis Color Change ~7 Day Color DYE (Reference Point) Analysis Change Analysis Name L* a* b* ΔL* Δa* Δb* ΔE* ΔL* Δa* Δb* ΔE* FD&C 59.18 4.14 58.68 0.12 −0.5 −1.78 1.86 −1.94 2.70 −0.82 3.44 Yellow 5 D&C 33.83 31.45 13.40 0.29 0.02 1.07 1.11 0.40 0.23 1.28 1.36 Red 30

Example 4 General Synthesis of Carbonate Catalyst by Reacting Base and Carbon Dioxide.

Tributylmethylammonium chloride (TBMA Cl), (10 g) was dissolved in ethanol (8.7 g) and mixed with a 20 wt. % solution of potassium ethoxide in ethanol (17.8 g) in 1:1 molar ratio. Anhydrous ethanol was used. The mixture was allowed to mix under agitation for 30 min, and was then centrifuged at 5000 rpm for 15 min to remove potassium chloride precipitate. The concentration of tributylmethylammonium ethoxide was determined potentiometrically by titrating it against 0.1 N HCl solution. Dry carbon dioxide gas was passed through the tributylmethylammonium ethoxide solution with stirring for 1 hour as to obtain the desired initiator. The tributylmethylammonium ethylcarbonate (TBMA EC) solution in ethanol is light yellow in color and is characterized by means of acid and base titrations (potentiometric and with indicator) and NMR.

A tributylmethylammonium isopropylcarbonate (TBMA IPC) catalyst solution was prepared in a similar manner. Tributylmethylammonium chloride was reacted with potassium tert-butoxide in essentially water free isopropanol followed by centrifugation prior to passing carbon dioxide through the solution. NMR analysis confirmed isopropylcarbonate as the anionic species.

Example 5 Malonate Resin (II) Synthesis

A 3 L reactor was charged with 700.0 g of diethyl malonate, 619.8 g of 1,6-hexanediol (HDO) and 227.5 g of ethyl acetoacetate (EAA). The reactor was equipped with a Dean-Stark apparatus, overhead mechanical stirrer, nitrogen flow and heating equipment. The mixture was heated to about 120° C. with stirring under nitrogen and then 0.62 g of phosphoric acid was added. Temperature was then increased to 145° C. and ethanol started to distill at this temperature. Temperature was then stepwise increased to 180° C. and continued until ethanol distillation stopped. In total, 588 ml of ethanol was collected. The reaction was then cooled to 120° C. and vacuum was applied for 4 hours while driving molecular weight. The final product is clear with less than 0.1% of residual monomer. GPC analysis showed Mw/Mn (PD) of 4143/1792 (2.31) in g/mole.

Example 6 Malonate Resin (III) Synthesis

A 5 L reactor was charged with 2075.0 g (8.12 moles) of diethyl malonate (DEM), 1182.9 g (9.74 moles) of 1,3-propanediol (PD) and 674.4 g (3.25 moles) of ethyl acetoacetate (EAA). The reactor was equipped with a Dean-Stark apparatus, overhead mechanical stirrer, nitrogen flow and heating equipment. The mixture was heated to about 120° C. with stirring under nitrogen and then 1.57 g of phosphoric acid was added. Temperature was then increased to 145° C. and ethanol started to distill at this temperature. Temperature was then stepwise increased to 180° C. and continued until ethanol distillation stopped. In total, 1396 g of ethanol was collected. The reaction was then cooled to 120° C. and vacuum was applied for 4 hours while driving the molecular weight. The final product was very light yellow in color with less than 0.5% of residual monomer. GPC analysis showed Mw/Mn (PD) of 2337/1507 (1.55) in g/mole and malonate methylene equivalent molecular weight of 169 g/mole.

Example 7 Basic Clear Nail Polish Formulation

The TBMA EC solution of Example 4 was tested as an initiator catalyst. In a vial, 2.0 g of the malonate resin II of Example 5 was mixed with 2.68 g of DTMPTA, 0.4 g of BA and 0.80 g of the TBMA EC solution was added. The complete formulation was mixed well prior to observing gel time and applying a 3 mil test film on a polycarbonate substrate to test coating curing behavior. The ambient relative humidity was low at 15%, while the temperature was 21° C. The absolute humidity was 2.8 [g/m³]. A similar test was carried out with the TBMA IPC catalyst using 0.90 g of the TBMA IPC solution to keep molar amounts of catalyst constant versus the resin. Data in Table 3 shows that a notably shorter gel time for the isopropanol based catalyst was observed in comparison to the ethanol based catalyst.

TABLE 3 Tack free Gel time Catalyst Solvent time [m:s] [min] TBMA EC Ethanol 1:30 50 TBMA IPC 2-Propanol 2:00 25

Example 8

The procedure as per Example 7 was repeated except that varying amounts of dimethylammonium dimethylcarbamate (DMADMC) were added to the TBMA EC solution prior to adding said solution to the resin/DTMPTA solvent mix. The DMADMC was obtained from commercial sources and purity was checked via NMR. DMADMC is the reaction product between dimethylamine and carbon dioxide in a 2:1 molar ratio, albeit small deviations from this stoichiometry are possible in commercially available DMADMC materials. Such commercial materials may also contain ammonium carbonates depending on source purity. All ingredient amounts were kept the same and the DMADMC amount is thus on top of the formulation. Only in experiment #4, was DMADMC added to the resin/DTMPTA solvent mix rather than to the catalyst solution. The complete formulation was mixed well prior to observing gel time and applying a 3 mil test film on a polycarbonate substrate to test coating curing behavior. The ambient relative humidity was 48% while the temperature was 21° C. The absolute humidity was 8.8 [g/m3]. Results in Table 4 shows that addition of DMADMC greatly increases gel time while the tack free time only marginally increases unless significant amounts of DMADMC in excess to the catalyst are added. No significant effect of DMADMC addition on film properties were noted after cure.

TABLE 4 DMADMC/carbonate Tack free # catalyst (molar ratio) time [m:s] Gel time 1 0 2:30 1 hr 2 0.5 2:20 12 hr 3 1 2:30 2 days 4 1 2:45 2 days 5 2 2:55 4 days 6 5 4:00 >4 days

Example 9 Red Nail Polish Formulation

A basic nail color formulation was prepared and evaluated per the general procedures as outlined in example 3, however, malonate resin II of example 5 was used to prepare a D&C Red 7 dye dispersion. The final overall formulation contained 0.167 g D&C Red 7 dye, 0.948 g resin II of example 5, 0.632 g resin III of example 6, 0.837 g ethanol and 2.449 g DTMPTA. 1.1604 g of TBMA EC catalyst solution of example 4 was used to cure the formulation. Another such formulation was prepared except that 4 wt % water (relative to the total weight of the formulation) was added to this second formulation. All formulations were mixed well and then a 3 mil test film was applied on a polycarbonate substrate to test the curing behavior and coating final color. The relative humidity and temperature was kept constant as the films cured and the absolute humidity was 9.4 [g/m³]. Data in Table 5 shows that significant and undesirable color change occurs as water is added to the formulation.

TABLE 5 Water Tack free content, time, # wt. % [m:s] L* a* b* ΔE* Color 1 0 2:15 42.7 51.1 32.2 — Red/Orange 2 4 2:30 51.5 46.1 47.6 18.5 Orange/Yellow

Example 10 Red Nail Polish Formulation

The procedure as per Experiment 9 was repeated except that a D&C Red 33 was used as pigment to color the coating formulation. Data in Table 6 shows that color does not change as water is added to the formulation.

TABLE 6 Water Tack free content, time, # wt. % [m:s] L* a* b* ΔE* Color 1 0 1:45 44.28 47.44 19.19 — Red 2 4 2:15 44.17 47.22 19.25 0.3 Red

Example 11 Red Nail Polish Formulation

The procedure as per Experiment 9 was repeated except that a D&C Red 7 Calcium Lake was used as pigment. No additional water was added and 0.967 g of the TBMA EC catalyst solution of Example 4 was used. However, two different rooms with controlled humidity and temperatures were utilized to explore influence of low-to-medium and high relative humidity levels coupled with temperatures at about 20 and 25° C. respectively. This represents nail polish application use under normal and high humidity conditions. The complete formulation was mixed well, split in two and then 3 mil test films were applied on polycarbonate substrates to test curing behavior and coating final color. Results in Table 7 show drastic color changes for this D&C Red 7 Calcium Lake system as the nail coating cures at high humidity conditions—the color changes notably as the film cures. The color displayed by the film cured under low humidity conditions is considered the normal D&C Red 7 Calcium Lake color and no color change is observed during cure.

TABLE 7 Absolute Tack free humidity, time, # [g/m3] [m:s] L* a* b* ΔE* Color 1a 2.9 <2:30 37.39 46.14 18.23 — Dark Red 1b 10.5 <2:30 62.31 36.09 62.28 51.6 Yellow

Example 12 Red Nail Polish Formulation

The procedure as per experiment 11 was repeated exploring a variety of D&C and FD&C dyes. Data is presented in Table 8. D&C Red No. 17 and D&C Red No. 36 are incompatible with the nail polish chemistry as significant color changes are observed during the curing process at both humidity levels. D&C Red No. 7 and D&C Red No. 33 show observable and undesirable color changes during cure at higher humidity levels. D&C Red No. 6 does show a measurable color difference for the cured films but the color change during cure is less apparent. The other dyes show minor color differences when the cured films are compared but no visible color change during the cure is observed. Since the formulation is split in two and brought into a higher temperature and humidity environment during the experiment, it is speculated that condensation of water at high humidity levels on the colder film may potentially have affected film surface and therewith moved the color CIELAB results slightly yet systematically. Since only a minor color change was observed for these dyes, the panels prepared under high humidity conditions were re-measured one week later to assess dye color stability. Results shown in Table 9 show minor color changes for the cured films and these dyes are assessed as stable.

TABLE 8 Tack Absolute free Dye humidity, time, # Dye class [g/m3] [m:s] L* a* b* ΔE* Color 1a D&C Red Monoazo 7.0 1.5 51.96 51.52 39.82 — Red/Orange No. 6 1b D&C Red Monoazo 19.5 2.5 52.24 48.51 47.04 7.8 Red/Orange No. 6 2a D&C Red Monoazo 7.2 1.5 38.93 46.25 23.28 — Red No. 7 2b D&C Red Monoazo 20.0 7 55.05 42.22 53.41 34.4  Yellow No. 7 3a D&C Red Diazo 8.8 1.5 Significant and immediate color change/dye No. 17 breakdown to brown 3b D&C Red Diazo 19.6 2 Significant and immediate color change/dye No. 17 breakdown to brown 4a D&C Red Xanthene 9.0 2.5 61.06 55.69 35.84 — Red/Orange No. 21 4b D&C Red Xanthene 19.3 3.5 61.76 56.05 31.57 4.3 Red/Orange No. 21 5a D&C Red Xanthene 9.0 2 63.58 56.03 24.02 — Red/Orange No. 22 5b D&C Red Xanthene 19.5 5 63.42 56.51 28.57 4.6 Red/Orange No. 22 6a D&C Red Xanthene 8.5 1.5 58.76 70.41 −5.17 — Bright No. 28 Red/Pink 6b D&C Red Xanthene 20.8 4 55.99 71.61 −2.15 4.3 Bright No. 28 Red/Pink 7a D&C Red Indigoid 9 1.5 51.41 43.81 13.45 — Red No. 30 7b D&C Red Indigoid 20.8 2.5 53.61 39.86 12.71 4.6 Red No. 30 8a D&C Red Monoazo 8.7 1.5 34.31 42.79 −3.88 — Dark Red No. 33 8b D&C Red Monoazo 21 4 40.23 39.3 −11.74 10.4  Dark Red No. 33 9a D&C Red Monoazo 9.0 1.5 Significant and immediate color change/dye No. 36 breakdown to black 9b D&C Red Monoazo 20.9 2.0 Significant and immediate color change/dye No. 36 breakdown to black 10a  FD&C Monoazo 8.6 1.5 46.19 50.28 30.66 — Red Red No. 40 10b  FD&C Monoazo 19.6 2.5 47.79 49.64 28.03 3.1 Red Red No. 40

TABLE 9 # Dye Dye class L* a* b* ΔE* Color 1b D&C Red Monoazo 52.24 48.51 47.04 Red/ No. 6 Orange 1c D&C Red Monoazo 52.44 49.48 48.02 1.4 Red/ No. 6 Orange 4b D&C Red Xanthene 61.76 56.05 31.57 Red/ No. 21 Orange 4c D&C Red 2 Xanthene 63.02 57.09 31.37 1.6 Red/ No. 1 Orange 5b D&C Red Xanthene 63.42 56.51 28.57 Red/ No. 22 Orange 5c D&C Red Xanthene 64.30 56.14 27.50 1.4 Red/ No. 22 Orange 6b D&C Red Xanthene 55.99 71.61 −2.15 Bright No. 28 Red/ Pink 6c D&C Red Xanthene 56.77 71.71 0.57 2.83 Bright No. 28 Red/ Pink 7b D&C Red Indigoid 53.61 39.86 12.71 Red No. 30 7c D&C Red Indigoid 53.6 40.51 13.07 0.74 Red No. 30 8b D&C Red Monoazo 40.23 39.3 −11.74 — Dark No. 33 Red 8c D&C Red Monoazo 39.65 40.02 −10.70 1.4 No. 33 10b  FD&C Red Monoazo 47.79 49.64 28.03 — Red No. 40 10c  FD&C Red Monoazo 45.45 47.84 25.86 3.7 Red No. 40

List of Chemical Acronyms Used in the Examples

BA butyl acetate DEM diethyl malonate DEtC diethyl carbonate DMADMC dimethylammonium dimethylcarbamate DTMPTA di-trimethylolpropane tetraacrylate EAA ethyl acetoacetate HDO 1,6-hexanediol PD 1,3-propanediol PEG 300 polyethylene glycol, Mw = 300 TBA OH tetrabutylammonium hydroxide TBMA Cl tributylmethylammonium chloride TBMA EC tributylmethylammonium ethylcarbonate TBMA IPC tributylmethylammonium isopropylcarbonate TMPTA trimethylolpropane triacrylate

The present disclosure may be embodied in other specific forms without departing from the spirit or essential attributes of the invention. Accordingly, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the disclosure. Although the foregoing description is directed to the preferred embodiments of the disclosure, it is noted that other variations and modification will be apparent to those skilled in the art, and may be made without departing from the spirit or scope of the disclosure. 

What is claimed:
 1. A nail polish composition containing a crosslinkable coating composition comprising: ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and a carbonate initiator of Formula (1)

wherein R₇ is selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms; and A^(n+) is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A^(n+) is not an acidic hydrogen; at least one colorant independently selected from the group consisting of (i) a dye; (ii) an inorganic pigment; or an (iii) a lake; and optionally further comprising ammonium carbamate (H₂NR₈R₉+—OC═ONR₈R₉), wherein R₈ R₉ are each independently selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.
 2. The nail polish composition according to claim 1, wherein the dye is selected from the group consisting of D&C Red 21, D&C Red No. 22, D&C Red No. 28, D&C Red No. 30, D&C Red No. 40, D&C Red No. 33, D&C Black No. 2, D&C Yellow No. 5, D&C Green No. 5, Annatto, Caramel and combinations thereof.
 3. The nail polish composition according to claim 1, wherein the inorganic pigment is selected from the group consisting of red iron oxide; yellow iron oxide; titanium dioxide; brown iron oxide; chromium oxide green; iron blue (ferric ferrocyanide blue); ultramarine blue; ultramarine violet; ultramarine pink; black iron oxide; bismuth oxychloride; aluminum powder; manganese violet; mica; bronze powder; copper powder; guanine and combinations thereof.
 4. The nail polish composition according to claim 1, wherein the lake is a D&C lake.
 5. The nail polish composition according to claim 1, wherein ingredient A is selected from the group consisting of compounds, oligomers or polymers.
 6. The nail polish composition according to claim 5, wherein the ingredient A is independently selected from a malonate group containing compound, a malonate group containing oligomer, a malonate group containing polymer, an acetoacetate group containing compound, an acetoacetate group containing oligomer, an acetoacetate group containing polymer or combinations thereof.
 7. The nail polish composition according to claim 6, wherein the malonate group containing compound, malonate group containing oligomer, malonate group containing polymer, an acetoacetate group containing compound, acetoacetate group containing oligomer, or acetoacetate group containing polymer are each selected from the group consisting of: polyurethanes, polyesters, polyacrylates, epoxy polymers, polyamides, polyesteramides or polyvinyl polymers, wherein such compounds, oligomers or polymers have a malonate group or acetoacetate group located in a main chain of such compound or oligomer or polymer or a side chain of such compound or oligomer or polymer.
 8. The nail polish composition according to claim 7, wherein ingredient B is selected from the group consisting of acrylates, fumarates, maleates and combinations thereof.
 9. The nail polish composition according to claim 8, wherein the acrylate is independently selected from the group consisting of hexanediol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate, bis(2-hydroxyethyl acrylate), trimethylhexyl dicarbamate, bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyl dicarbamate, bis(2-hydroxylethyl acrylate) methylene dicyclohexyl dicarbamate and combinations thereof.
 10. The nail polish composition according to claim 9, wherein ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least two pendant ethylenically unsaturated groups each activated by an electron-withdrawing group.
 11. The nail polish composition according to claim 10, wherein ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least one pendant acryloyl functional group.
 12. The nail polish composition according to claim 1, further comprising an ingredient D having one or more reactive protons that are more acidic than the two protons of ingredient A, with respect to pKa.
 13. The nail polish composition according to claim 12, wherein the one or more reactive protons of ingredient D are less acidic than the ammonium cation of the optional ammonium carbamate, with respect to pKa.
 14. The nail polish composition according to claim 1, further comprising water concentration selected from the group consisting of less than 10 wt. %, less than 5 wt. %; less than 1 wt. %; less than 0.1 wt. %; less than 0.01 wt. % water.
 15. The nail polish composition coating composition according to claim 1, further comprising an organic solvent.
 16. The nail polish composition according to claim 15, wherein the organic solvent is independently selected from the group consisting of an alcohol, ester, ether, glycol ether, ketone, aromatic and combinations thereof.
 17. The nail polish composition according to claim 16, wherein the alcohol is independently selected from the group consisting of methanol, ethanol, iso-propanol, butanol, iso-butanol, t-butanol and combinations thereof.
 18. The nail polish composition according to claim 1, wherein A^(n+) is a monovalent quaternary ammonium compound of Formula (2)

wherein R₃, R₄ and R₅ are independently selected from linear or branched alkyl chains having from 1 to 22 carbon atoms; or 1 to 8 carbon atoms; or 1 to 4 carbon atoms and combinations thereof and wherein R₆ is independently selected from the group consisting of: methyl, an alkyl group having from 2 to 6 carbon atoms or a benzyl group.
 19. The nail polish composition according to claim 1, wherein the dormant carbonate initiator initiates Michael Addition to achieve crossing linking when the crosslinkable coating composition is applied to a surface.
 20. The nail polish composition according to claim 1, wherein ingredient A, ingredient B and the carbonate initiator are contained in a container having two or more chambers, which are separated from one another.
 21. The nail polish composition according to claim 20, wherein ingredient A and ingredient B are contained in separate chambers to inhibit any reaction.
 22. The nail polish composition according to claim 20, wherein the carbonate initiator is contained in the chamber having ingredient A, and optionally containing CO₂ and/or ammonium carbamate.
 23. The nail polish composition according to claim 20, wherein ingredient A and ingredient B are contained in the same chamber and the carbonate initiator is contained in a separate chamber to inhibit any reaction and said separate chamber optionally containing CO₂ and/or ammonium carbamate.
 24. The nail polish composition according to claim 1 wherein ingredient A and ingredient B and carbonate initiator are contained in a container having a single chamber, wherein the container optionally (i) contains CO₂ and/or ammonium carbamate.
 25. The nail polish composition according to claim 20, further comprising at least one solvent selected from the group consisting of acetone, ethyl acetate, butyl acetate, isopropyl alcohol, ethanol, methyl ethyl ketone, and combinations thereof.
 26. The nail polish composition according to claim 1, further comprising a rheological additive to modify rheology.
 27. The nail polish composition according to claim 1, further comprising a wetting agent.
 28. The nail polish composition according to claim 1, further comprising an adhesion promotor.
 29. The nail polish composition according to claim 1, further comprising nitrocellulose, polyvinylbutyral, tosylamide formaldehyde and/or tosylamide epoxy resins.
 30. The polymerizable nail coating composition according to claim 1, further comprising a cellulose acetate alkylate selected from the group consisting of cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof. 